TWI430997B - Indane compounds - Google Patents

Description

Dihydroanthracene compound

The present invention relates to an indoline compound having at least one tetrahydropyran ring, as shown in Formula I: Wherein R ¹ represents H, an alkyl group having up to 15 carbon atoms, which is unsubstituted, monosubstituted with CN or CF ₃ or at least monosubstituted with halogen, further wherein one or more CH ₂ groups of these alkyl groups Can be independently -O-, -CH=CH-, -C≡C-, -S-, -CO-, -CO-O- , -O-CO- or -O-CO-O is displaced such that the oxygen atoms are not directly connected to each other, and A ¹ and A ² are independent of each other, and represent (a) trans-1,4-cyclohexylene, and further, one of them Or a plurality of non-adjacent CH ₂ groups may be replaced by -O- and/or -S-. (b) 1,4-phenylene, in addition, one or more of the CH groups may be substituted by N, (c) 1,4-cyclohexene, and (d) from 1,4-bicyclo[ 2.2.2] a group of octyl, piperidine-1,4-diyl, cyclobutane-1,3-diyl, spiro[3.3]heptane-2,6-diyl, (e) A price group selected from: Wherein Y, Y ¹ , Y ² and Y ³ are independent of each other, and may be H, F, Cl, CN, NCS, SF ₅ , OCF ₃ , OCHF ₂ , OCH ₂ F, OCH ₃ , CH ₃ , CH ₂ F, CHF ₂ or CF ₃ , one or more double bonds may be replaced by a single bond, and M, M ¹ or M ² represents -O-, -S-, -CH ₂ -, -CHF- or -CF ₂ -, wherein the hetero atom Not directly connected to each other, wherein the groups (a) to (d) may be substituted by one or more (particularly 1 to 2) fluorine atoms, and if the group of the group (e) is asymmetric , there may be two orientations, B represents a divalent group, such as the formula: Z ¹ , Z ² or Z ³ are independent of each other and represent -CO-O-, -O-CO-, -CH ₂ O-, -OCH ₂ -, -CH ₂ CH ₂ -, -CH=CH-, -CH =CF-, -CF=CH-, -CF=CF-, -CHF-CHF-, -CH ₂ -CHF-, -CHF-CH ₂ -, -C≡C-, -(CH ₂ ) ₄ -, -CF ₂ O-, -OCF ₂ -, -C ₂ F ₄ -, -CH=CH-CH ₂ CH ₂ -, -CH ₂ CH ₂ OCF ₂ - or a single bond, X ¹ and X ² are independent of each other, Represents H, Cl, F, CN, NCS, SF ₅ or an alkyl group having up to 8 carbon atoms, and further wherein the CH ₂ group may be replaced by -O-, -CH=CH- or -C≡C-, wherein One or more hydrogen atoms may be replaced by F or Cl, and m, n are independent of each other, representing 0, 1, or 2.

Further, the present invention relates to the use of these compounds as liquid crystal dielectric components, and to liquid crystal display elements and electro-optical display elements containing the liquid crystal medium according to the present invention.

Depending on the principle of the torsion unit, the guest-host effect, the alignment phase distortion effect or the dynamic scattering effect, the compounds of the formula I can be used as constituents of liquid-crystalline media, in particular for displays.

Document JP 62-181247 describes 5,6-cyanoindoline derivatives with an alkyl group at the 2-position or an alkylcyclohexyl group via the ethylene bridge. JP 62-195355 discloses corresponding 5-cyanoindoline derivatives having only one CN group. DE 4303634 A1 discloses corresponding 5,6-difluoroindoline derivatives which have a mesogenic group at the 2-position. Similar 5-substituted dihydroindoles and 6-substituted dihydroindoles for liquid crystal mixtures can also be found in DE 4409526 A1, JP 2004-277589 A and JP 2005-15688 A, in which tetrahydropiperidyl is generally not mentioned. The quaternary-2,5-diyl ring serves as a partial structure of the disclosed compound.

The object of the present invention is to find novel stable compounds which are suitable as components of liquid crystal media, especially for TN, STN, IPS and active matrix displays.

Another object of the present invention is to provide a compound having high dielectric anisotropy Δ ε, low optical anisotropy Δn, high definition point, and low rotational viscosity γ1. Furthermore, the compounds according to the invention should be thermally stable and photochemically stable. Moreover, the compounds according to the invention can be applied to liquid crystal mixtures which can be dissolved in conventional mixtures without shrinking or even improving their liquid crystal phase range.

We have found that the indoline derivatives according to the invention are particularly suitable as components of liquid crystal media. They can be used to obtain stable liquid crystal media, especially for TN-TFT, STN and IPS liquid crystal displays. The compounds according to the invention are chemically stable, thermally stable, and resistant to (ultraviolet) light. They are colorless in the pure state. They also have the property of strong positive dielectric anisotropy Δε. Due to this characteristic, the threshold voltage must be lowered when used for the optical switching element. Furthermore, these compounds have an advantageous, ie low, rotational viscosity value. These compounds according to the invention have the additional advantage over the cyclohexane derivatives that the tetrahydropyranose ring has a high degree of polarization and does not adversely affect optical properties and polarizability. An advantage of tetrahydropyran derivatives over the 1,4-phenylene rings attached to the indoline 2-position is that they employ a chair configuration which allows the molecules to stretch more.

Liquid-crystalline media have very low optical anisotropy, which is particularly important for applications in reflection and transflective, ie, the LCD has no backlighting or only auxiliary backlighting when applied. In this respect, we can also obtain a mixture of liquid crystals and derivatives according to the invention, which has a very low optical anisotropy or a slightly positive dielectric anisotropy to a strong positive dielectric anisotropy. In particular, we can simultaneously obtain low optical anisotropy and high positive dielectric anisotropy.

From a different application point of view, the indoline derivatives provided in accordance with the present invention typically broadly expand the range of compounds suitable for preparing liquid crystal mixtures.

The compound according to the invention forms a liquid crystal mesophase in the mixture in a temperature range which is advantageous for electro-optical applications. Liquid crystal media having a broad nematic phase range can be prepared from the compounds according to the invention and derivatives thereof.

Dihydroanthracene derivatives are widely used. By selecting different substituents, these compounds can serve as a matrix material mainly contained in the liquid crystal medium. However, it is also possible to add other liquid-like matrix material compounds to the compounds according to the invention in order, for example, to change the dielectric anisotropy and/or optical anisotropy of such dielectrics, and/or to reach their optimum threshold voltage and/or Or its stickiness.

The invention relates to compounds of the formula I and to the use of these compounds as constituents of liquid-crystalline media. Furthermore, the invention relates to liquid-crystalline media containing at least one compound of the formula I, and to liquid-crystalline display elements, in particular electro-optical display elements containing such media.

The groups X ¹ and X ² in the formula I and the subformula are preferably H, Cl, F, CF ₃ or OCF ₃ . Further, preferably at least one of the substituents X ¹ and X ² is not hydrogen and is preferably selected from the group consisting of substituents Cl, F, CF ₃ and OCF ₃ . Likewise, X ¹ and X ^{2 are} preferably the same. These derivatives are particularly easy to prepare. It is particularly preferred when X ¹ and X ^{2 are the} same and represent F, Cl or CN, and in particular all represent F. These latter compounds generally have high dielectric anisotropy.

Ring systems A ¹ and A ² (if present) may each have one of the meanings described above. If they occur more than once, if m or n is greater than 1, each ring can have a different meaning. If the groups (a) to (e) are shown to be asymmetric, there are two possible orientations. Preferably, the orientation is such that the two poles of the ring are arranged in the same direction and parallel to the two poles of the indoline ring. In practice, this means that the presence of heteroatoms such as halogen, nitrogen or oxygen is oriented substantially towards the longitudinal axis of the molecule. Specifically, the substituents Y, Y ¹ , Y ³ and Y ⁴ of the ring system in (e) are directed to the direction of the indoline ring.

The groups Z ¹ , Z ² and Z ³ have one of the meanings as described above. If they occur more than once, if m or n is greater than 1, each group can also have a different meaning. Z ¹ and Z ² preferably represent a single bond, -CH ₂ CH ₂ -, -CH=CH- or -CF ₂ O-, especially a single bond.

The group Z ³ , n = 0, preferably does not represent a group of the formula -C=C-. Preferred definitions for Z ³ are -CO-O-, -O-CO-, -CH ₂ O-, -OCH ₂ -, -CH ₂ CH ₂ -, -CH=CF-, -CF=CH-, - CF=CF-, -CHF-CHF-, -CH ₂ -CHF-, -CHF-CH ₂ -, -C≡C-, -CF ₂ O-, -OCF ₂ -, -C ₂ F ₄ -, - CH=CH-CH ₂ CH ₂ -, -CH ₂ CH ₂ OCF ₂ - or a single bond, especially a single bond.

The sum of the subscripts n and m in formula I should be 0, 1, 2 or 3, preferably 0, 1 or 2, especially 0 or 1. The subscripts m and n are preferably independent of each other, indicating 0 or 1.

For simplicity, the following A ³ represents a group of the following formula:

Thus the compound of formula I is also represented by the formula: R ¹ -[A ¹ -Z ¹ ] _m -B-Z ³ -[A ² -Z ² ] _n -A ³ I

Thus a compound of formula I includes a compound of formula Ia and Ib having two rings (herein the "ring" also includes a ring system having a plurality of subrings, such as indoline): R ¹ -B-A ³ Ia R ¹ -B -Z ³ -A ³ Ib

Preferred compounds having three rings selected are those of the formula Ic and Ih: R ¹ -A ¹ -B-A ³ Ic R ¹ -A ¹ -Z ¹ -B-A ³ Id R ¹ -A ¹ - B-Z ³ -A ³ Ie R ¹ -B-A ² -A ³ If R ¹ -B-Z ³ -A ² -A ³ Ig R ¹ -B-A ² -Z ² -A ³ Ih

Among these compounds, the compounds of the formula Ic and If are particularly preferred.

Preferred compounds having four rings are compounds of the formula Ii to the formula Ir: R ¹ -A ¹ -A ¹ -B-A ³ Ii R ¹ -A ¹ -Z ¹ -A ¹ -B-A ³ Ij R ¹ -A ¹ -A ¹ -Z ¹ -B-A ³ Ik R ¹ -A ¹ -A ¹ -B-Z ³ -A ³ Il R ¹ -A ¹ -B-A ² -A ³ Im R ¹ -A ¹ -B-A ² -Z ² -A ³ In R ¹ -A ¹ -B-Z ³ -A ² -A ³ Io R ¹ -B-A ² -A ² -A ³ Ip R ¹ - B-A ² -A ² -Z ² -A ³ Iq R ¹ -B-A ² -Z ² -A ² -A ³ Ir

Among these compounds, compounds of the formulae Ii, Im and Ip are particularly preferred.

Preferred are compounds of formula I and all sub-formulae thereof, wherein A ¹ and/or A ² represents a cyclohexane-1,4-diyl, 1,4-cyclohexenylene, tetrahydropyran-2 , 5-diyl, 1,4-phenylene, 1,4-phenylene mono- or di-substituted by fluorine or a group as defined in formula (d) and (e).

A ¹ and A ² preferably represent a divalent group selected from the group consisting of:

R ¹ preferably represents an alkyl group, an alkoxy group, an alkenyl group or an alkenyloxy group having up to 7 carbon atoms, more preferably 1 to 5 C alkyl groups or 2 to 5 C alkenyl groups.

If R ¹ represents an alkyl group and/or an alkoxy group, it may be straight-chain or branched. It is preferably linear and has 1, 2, 3, 4, 5, 6 or 7 carbon atoms, and thus preferably represents methyl, ethyl, propyl, butyl, pentyl, heptyl, hexyl, Oxyl, propoxy, butoxy, pentyloxy, hexyloxy or heptyloxy, further denoted octyl, decyl, decyl, undecyl, dodecyl, tridecyl , tetradecyl, pentadecyl, methoxy, octyloxy, nonyloxy, nonyloxy, undecyloxy, dodecyloxy, tridecyloxy or tetradecyloxy .

If R ¹ represents an alkyl group in which one CH ₂ group has been replaced by -CH=CH-, it may be straight-chain or branched. It is preferably a linear chain of 2 to 10 carbon atoms. Therefore, it particularly denotes prop-1- or 2-alkenyl, but-1-, 2- or 3-alkenyl, pent-1-, 2-, 3- or 4-alkenyl, hex-1-, 2 -, 3-, 4- or 5-alkenyl, hept-1-, 2-, 3-, 4-, 5- or 6-alkenyl, oct-1-, 2-, 3-, 4-, 5- -, 6- or 7-yl, 壬-1-, 2-, 3-, 4-, 5-, 6-, 7- or 8-alkenyl, 癸-1-, 2-, 3-, 4- , 5-, 6-, 7-, 8- or 9-alkenyl.

If R ¹ represents an alkyl group and one of the CH ₂ groups has been replaced by -O- and one is replaced by -CO-, these groups are preferably adjacent. These groups therefore contain a decyloxy-CO-O- or an oxycarbonyl-O-CO- group. These are preferably straight chains having 2 to 6 carbon atoms. Therefore, they are specifically represented by ethoxycarbonyl, propenyloxy, butyloxy, pentyloxy, hexyloxy, ethoxymethyl, propyloxymethyl, butyloxy , pentyloxymethyl, 2-ethyloxyethyl, 2-propoxyethyl, 2-butoxyethyl, 3-ethyloxypropyl, 3-propoxy Propyl, 4-ethenyloxybutyl, methoxycarbonyl, ethoxycarbonyl, propoxycarbonyl, butoxycarbonyl, pentyloxycarbonyl, methoxycarbonylmethyl, ethoxycarbonylmethyl, ethoxycarbonylmethyl , Butoxycarbonylmethyl, 2-(methoxycarbonyl)ethyl, 2-(ethoxycarbonyl)ethyl, 2-(propoxycarbonyl)ethyl, 3-(methoxycarbonyl)propyl, 3-( Ethoxycarbonyl)propyl, 4-(methoxycarbonyl)butyl.

If R ¹ represents an alkyl group in which one CH ₂ group is replaced by an unsubstituted or substituted CH=CH and an adjacent CH ₂ group has been replaced by CO or CO-O or O-CO, the alkyl group may It is straight or branched. It is preferably a linear chain of 4 to 13 carbon atoms. Therefore, it particularly means propylene oxime methyl, 2-propenyl oxyethyl, 3-propenyl oxypropyl, 4-propenyloxybutyl, 5-propenyloxypentyl, 6-propenyloxyhexyl, 7-Allyloxyheptyl, 8-propenyloxyoctyl, 9-propenyloxycarbonyl, 10-propenyloxymethyl, methacryloxymethyl, 2-methylpropenyloxyethyl, 3-Methyl propylene oxime propyl, 4-methyl propylene oxy butyl, 5-methylpropenyl oxypentyl, 6-methylpropenyloxyhexyl, 7-methylpropenyloxyheptyl, 8 - Methyl propylene oxiranyl, 9-methyl propylene oxime.

If R ¹ represents an alkyl or alkenyl group which is monosubstituted by CN or CF ₃ , the group is preferably a straight chain, and the substitution site is preferably at the ω position.

If R ¹ represents an alkyl or alkenyl group which is monosubstituted by halogen, the group is preferably a straight chain, and the halogen is preferably F or C1. If it is multi-substituted, the halogen is preferably F. The resulting group also includes perfluorinated groups. When monosubstituted, the fluoro or chloro substituent may be in any desired position, but is preferably in the ω position.

Compounds of formula I having pendant groups R ¹ suitable for polymerization are suitable for the preparation of liquid crystal polymers.

Compounds of formula I containing branched pendant groups R ¹ may sometimes be more important because they have better solubility in conventional liquid crystal matrix materials, but are particularly suitable as palmitic dopants if they are optically active. Such smectic compounds are suitable as components of ferroelectric materials.

For example, a compound of formula I having a S _A phase is suitable as a thermally addressable display.

Such branched chain groups usually contain at most one branch. Preferred branched groups R are isopropyl, 2-butyl (=1-methylpropyl), isobutyl (=2-methylpropyl), 2-methylbutyl, isopentyl (= 3-methylbutyl), 2-methylpentyl, 3-methylpentyl, 2-ethylhexyl, 2-propylpentyl, isopropoxy, 2-methylpropoxy, 2- Methylbutoxy, 3-methylbutoxy, 2-methylpentyloxy, 3-methylpentyloxy, 2-ethylhexyloxy, 1-methylhexyloxy and 1-methyl Heptyloxy.

Compounds of formula I having pendant groups R ¹ suitable for polycondensation are suitable for the preparation of liquid crystal polycondensates. Formula I includes the racemates and optical enantiomers of the compounds of Formula I, and mixtures thereof.

Among the compounds of the formula I and the subformulae thereof, it is preferred that at least one of the groups of the formula has a compound as defined above.

Among the compounds of the formula I, preferred are stereoisomers in which the cyclohexane ring is trans-1,4-disubstituted. The above general formula which can include many stereoisomers in all cases includes all possible stereoisomers.

Preferably, one of the compounds of formula I is as shown in subformulae I1 to I13.

Wherein R ¹ , X ¹ and X ^{2 are} as defined above, and L ₁ and L ₂ are independent of each other and represent H or F.

Among the compounds represented by the subformulas I1 to I13, particularly preferred are the compounds of the formulae I1, I2, I3 and I13.

The 1,4-cyclohexenyl group preferably has the following structure:

The compounds of formula I are prepared by known methods, as described in the literature (for example, authoritative works such as "Organic Chemical Methods" by Houben-Weyl, Georg-Thieme-Verlag, Stuttgart), under reaction conditions known to be suitable for the above reactions. preparation.

Known variants can also be used and will not be described again here.

Starting from a pure benzene derivative of the formula II, the compounds of the formula I according to the invention can be prepared via reactions known in the literature. One of the synthetic pathways is illustrated in Reaction Figure 1 and Reaction Figure 2:

The benzene derivative of formula II is brominated with N-bromosuccinimide (NBS) at the benzyl position, cyclized to the indane of formula IV using diethyl malonate, hydrolyzed and then decarboxylated. The remaining carboxylic acid is then reduced to an alcohol (preferably with borane) which is subsequently oxidized to the aldehyde, where pyridinium chlorochromate (PCC) is used. Formation of the aldehyde intermediate of formula V (reaction Figure 1).

The tetrahydropyran ring can be prepared from the aldehyde of the formula V, which is catalyzed by a Lewis acid (BiBr ₃ ) using (but optionally 2-substituted) but-3-en-1-ol (high allyl alcohol), first generated The bromotetrahydropyran of formula VI, the bromine substituent is then removed by reduction elimination, for example using hydrazine, followed by hydrogenation (reaction Figure 2). This reaction sequence produces a wide variety of compounds of formula VII. The substituent R ¹ may vary in a manner similar to that of Formula I. The desired high allyl alcohol can be prepared by standard methods (see also WO 2006/125527 A1, pages 27 to 29).

The substituent R ¹ in the reaction scheme 1 and the reaction scheme 2 can also be substituted with a compound of the formula I, by a group of the formula R ¹ -[A ¹ -Z ¹ ] _m -.

Thus, particular embodiments of the invention also include a process for the preparation of a compound of formula I wherein n is equal to zero, which comprises a dihydrofurfural of formula V.

Wherein X ¹ and X ^{2 are} as defined above and are reacted with the following formula: 3--3-en-1-ol Wherein R ¹ , A ¹ , Z ¹ and m are as defined above.

This reaction produces a substituted tetrahydropyran ring. The tetrahydropyran ring is at least 2-substituted with indoline, preferably 2,5-substituted by a 4-bromo substituent.

The reaction is preferably carried out in the presence of an acid, a protic acid or a Lewis acid, particularly a Lewis acid (BiBr ₃ or the like). Particularly suitable (Lewis) acids are disclosed on pages 7 to 9 of WO 2006/125527 A1, which is incorporated herein by reference.

The reaction product of the above process is usually a halotetrahydropyran derivative (see WO 2006/125527 A1 and Reaction Scheme 2). In a part of the process, the halogen tetrahydropyran derivative is reduced to form tetrahydropyran (see WO 2006/125526 A1). The reduction elimination method can be carried out in a number of different ways. Further details and specific examples of the reaction for the formation of a tetrahydropyran ring are disclosed in the above-mentioned publications WO 2006/125527 A1 and WO 2006/125526 A1. Specific embodiments in which the synthetic steps are disclosed and described are described in detail.

The compound according to the invention having another ring between the tetrahydropyran ring and the indoline ring can be synthesized according to the following reaction scheme 3.

Reaction Scheme 3. The exemplified compound (XIV) wherein n is greater than 0 in the formula I is prepared. The substituent is the same as in the formula I. The group R ¹ can also generally be represented by R ¹ -(A ¹ -Z ¹ ) _m -.

In the synthesis reaction shown in Figure 3, an indoline ring having an adjacent cyclohexane (XII) is formed in the first step reaction. This synthesis reaction is based on a known substituted indoline synthesis reaction. The cyclohexane ring can also be replaced by other substituents (e.g., phenyl). After reduction of the carbonyl group on the indoline ring to the alcohol, the resulting double bond is eliminated and hydrogenated, and the benzyl group is simultaneously cleaved upon the final hydrogenation. The resulting alcohol is oxidized to the aldehyde (XIII) using PCC. Using a modified Princes reaction, the resulting 4-bromotetrahydropyran is eliminated using hydrazine (eg, DBN) to form the dihydropyran, followed by hydrogenation of the product to obtain the final compound XIV (see Figure 2 for the reaction). Notes and citations, the disclosures of which are incorporated herein.

Publication WO 94/18285 A1 (pages 19 to 21) discloses more possible synthetic routes for the preparation of indoline structures and 2-position substitutions.

The liquid-crystalline medium according to the invention preferably comprises from 2 to 40, in particular from 4 to 30, constituents as components other than one or more compounds according to the invention. These media preferably comprise from 7 to 25 components in addition to one or more compounds according to the invention. These other components are preferably selected from nematic or nematic (singly or isotropic) materials, in particular the following types: azobenzene, benzylaniline, biphenyl, terphenyl, benzene Phenyl or hexyl acrylate, phenyl or cyclohexyl hexane carboxylic acid, phenyl or cyclohexyl cyclohexyl benzoate, phenyl or cyclohexyl Cyclohexylcyclohexane carboxylic acid, benzoic acid Cyclohexyl phenyl ester, cyclohexyl phenyl cyclohexane carboxylic acid or cyclohexyl phenyl cyclohexyl cyclohexane carboxylic acid, phenyl cyclohexane, cyclohexyl biphenyl, phenyl cyclohexyl cyclohexane, ring Hexylcyclohexane, cyclohexylcyclohexylcyclohexane, 1,4-dicyclohexylbenzene, 4,4'-dicyclohexylbiphenyl, phenylpyrimidine/cyclohexylpyrimidine, phenylpyridine/cyclohexylpyridine, phenyl/ Cyclohexyldioxane, phenyl/cyclohexyl 1,3-dithiane, 1,2-diphenylethane, 1,2-dicyclohexylethane, 1-phenyl-2-cyclohexylethane, 1-cyclohexyl-2-(4-phenylcyclohexyl)ethane, 1-cyclohexyl-2-biphenylethane, 1-phenyl-2-cyclohexylbenzeneethane, diphenyl which may be halogenated as desired Ethylene, benzyl phenyl , Tolans and substituted cinnamic acid of. It is also possible to fluorinate 1,4-phenylene in these compounds.

The most important compounds suitable as further constituents of the medium according to the invention have the characteristics of the formulae 1, 2, 3, 4, 5: R'-L-E-R" 1 R'-L-COO-E-R " 2 R'-L-OOC-E-R" 3 R'-L-CH ₂ CH ₂ -E-R" 4 R'-L-C≡C-E-R" 5

In the formulae 1, 2, 3, 4 and 5, L and E may be the same or different and independent of each other, each representing a divalent group selected from the group consisting of -Phe-, -Cyc-, -Phe-Phe- , -Phe-Cyc-, -Cyc-Cyc-, -Pyr-, -DiO-, -G-Phe-, -G-Cyc- and its enantiomers; wherein Phe represents unsubstituted or fluoro 1,4 - phenyl, Cyc represents trans-1,4-cyclohexylene or 1,4-cyclohexenyl, Pyr represents pyrimidine-2,5-diyl or pyridine-2,5-diyl, Dio represents 1 , 3-dioxane-2,5-diyl, G represents 2 (trans-1,4-cyclohexyl)ethyl.

One of the groups L and E is preferably Cyc, Phe or Pyr. E is preferably Cyc, Phe or Phe-Cyc. Preferably, the medium according to the invention comprises one or more ingredients selected from the group consisting of compounds of formulas 1, 2, 3, 4 and 5, wherein L and E are selectable from Cyc, Phe and Pyr; the medium comprises one or more other ones selected from the group consisting of a component of the compounds of the formulae 1, 2, 3, 4 and 5, wherein L and E are selected from Cyc, Phe and Pyr, and other groups are derived from -Phe-Phe-, -Phe-Cyc-, -Cyc-Cyc-, Selecting between -G-Phe- and -G-Cyc-; the medium may also optionally include one or more components selected from the group consisting of compounds of formulas 1, 2, 3, 4 and 5, wherein groups L and E are from -Phe Selected from -Cyc-, -Cyc-Cyc-, -G-Phe-, and -G-Cyc-.

In the subgroups of the compounds of the formulae 1, 2, 3, 4 and 5, R' and R" are independent of each other, and represent an alkyl group, an alkenyl group, an alkoxy group, an alkoxyalkyl group, an olefin having at most 8 carbon atoms. Or alkoxy group. Hereinafter, the subgroup is referred to as Group A, and the compounds are represented by Subformulas 1a, 2a, 3a, 4a and 5a. Among most of the compounds, R' and R" are different from each other, usually One group is an alkyl group, an alkenyl group, an alkoxy group or an alkoxyalkyl group.

The subgroup of compounds of the other formulas 1, 2, 3, 4 and 5 is referred to as group B, where R" represents F, Cl, NCS or -(O) _i CH _3-(k+1) F _k Cl ₁ , where i is 0 or 1, k+1 is 1, 2 or 3; compounds of R" having this meaning are represented by the subformulas 1b, 2b, 3b, 4b and 5b. It is a particularly preferred sub-formulas 1b, 2b, 3b, 4b and 5b compounds wherein R "represents _{F, Cl, NCS, CF 3} , OCHF 2 or OCF _3.

In the compounds of the formulae 1b, 2b, 3b, 4b and 5b, R' has the meanings designated by the compounds of the formulae 1a to 5a, preferably an alkyl group, an alkenyl group, an alkoxy group or an alkoxyalkyl group.

In another subgroup of compounds of formula 1, 2, 3, 4 and 5, R" represents -CN. This subgroup is referred to as group C, which is correspondingly represented by subformulae 1c, 2c, 3c, 4c and 5c In the compounds of the formulae 1c, 2c, 3c, 4c and 5c, R' has the meanings designated by the compounds of the formulae 1a to 5a, preferably an alkyl group, an alkenyl group, an alkoxy group or an alkenyl group.

In addition to the preferred compounds in Groups A, B, and C, other compounds of Formulas 1, 2, 3, 4, and 5 having the proposed substituent variations are also commonly employed. All of these materials can be obtained by methods known in the literature or the like.

In addition to the compounds of the formula I according to the invention, the medium according to the invention preferably comprises one or more compounds selected from group A and/or group B and/or group C. In the medium according to the invention, the weight ratio of the compound selected from the group is preferably Group A: 0 to 90%, preferably 20% to 90%, especially 30 to 90% Group B: 0 to 80%, preferably 10% to 80%, in particular 10% to 65% C group: 0 to 80%, preferably 5% to 80%, especially 5% to 50%, wherein in the medium according to the invention, selected from group A, The sum of the weight ratios of the compounds of Group B and Group C is preferably from 5% to 90%, particularly from 10% to 90%.

The medium according to the invention preferably comprises from 1% to 40%, in particular from 5% to 30%, of the compound according to the invention. Also preferred is a medium comprising more than 40%, especially from 45% to 90% of the compound. The medium preferably comprises two, three or four compounds according to the invention.

The medium according to the invention is prepared by conventionally known methods. It is usually preferred to heat to dissolve the components. Suitable additives can be used to modify the liquid crystal phase according to the present invention for use in the various types of liquid crystal display elements disclosed so far. Such additives are well known to those skilled in the art and are described in detail in the literature (H. Kelker/R. Hatz Liquid Crystal Handbook, 1980, Verlag Chemie, Weinheim). For example, a multicolor dye can be added to prepare a color guest host system or to add materials to alter the dielectric anisotropy, viscosity, and/or alignment of the nematic phase. In addition, stabilizers, antioxidants or nanoparticles can also be added.

The mixture according to the invention is suitable for TN, STN, ECB and IPS applications, in particular TFT applications.

The polarizing mirror, electrode substrate, and surface treatment electrode constituting the matrix display according to the present invention are the same as the general design of such a display. The term "general design" is broad and includes derivatives and modified products of matrix displays, especially matrix display elements based on polysilicon TFTs.

The following examples are intended to illustrate the invention but not to limit it. Above and below, the percentage data represents the weight percentage. All temperatures are in degrees Celsius. Mp represents the melting point, and cl.p. = clearing point. Further, C = crystalline state, N = nematic phase, Sm = smectic phase, I = isotropic phase. The data between these symbols represents the transition temperature, Δn represents optical anisotropy (589 nm, 20 ° C), and the flow viscosity v ₂₀ (mm ² /s), rotational viscosity γ1 [mPa. s] are measured at 20 ° C.

Physical parameters, physicochemical parameters and electro-optic parameters are determined using generally known methods, in particular "Merck LCD-Licristal" issued by Merck in Darmstadt, 1998. - Liquid crystal physical properties - Description of the method of measurement described in this booklet.

The dielectric anisotropy Δ ε of the individual substances was measured at 20 ° C and 1 kHz. To this end, 5-10% by weight of the test substance was dissolved in a positive dielectric mixture ZLI-4792 (Merck) for measurement, and the measured value was extrapolated to 100% concentration. The optical anisotropy Δn was measured at 20 ° C and 589.3 nm, and the rotational viscosity γ1 was measured at 20 ° C, both of which were obtained by linear extrapolation.

The "practical operation method" means that if water is added as appropriate, the mixture is extracted with dichloromethane, diethyl ether, methyl tert-butyl ether or toluene, the phases are separated, the organic phase is dried and evaporated, and the product is subjected to distillation under reduced pressure. , crystallization and / or chromatographic purification. The following abbreviations are used: DBN 1,5-diazabicyclo[4,3,0]non-5-ene (2,3,4,6,7,8-hexahydropyrrolo[1,2-a]pyrimidine DCM dichloromethane TLC thin layer chromatography RT room temperature MTB ether methyl tert-butyl ether THF tetrahydrofuran p-TsOH p-toluenesulfonic acid NBS N-bromobutaneimine

Example 1

Step 1.1

A solution of 6.9 g (10 mmol) of sodium nitrite dissolved in 12 ml of water was added dropwise at 5-10 ° C while stirring vigorously to 16.6 g (100 mmol) of aniline 1, 13 ml of concentrated hydrochloric acid and 15.4 g ( 140 mmol) of sodium tetrafluoroborate was dissolved in a mixture of 40 ml of water. After 1 hour at 25 ° C, the mixture was filtered. The solid was washed with ice water, methanol and methyl t-butyl ether and dried in vacuo. The diazonium salt is then decomposed by careful heating. The resulting residue was extracted twice with methyl tert-butyl ether. The extract was washed with a 10% sodium hydroxide solution and a saturated sodium chloride solution and dried over sodium sulfate. After evaporation, the residue was purified on silica gel.

Step 1.2

200 ml of dimethyl hydrazine and 18 g (110 mmol) of tetramethylammonium fluoride tetrahydrate were azeotropically dehydrated under nitrogen for 6 hours using 400 ml of cyclohexane. Subsequently, 17 g (100 mmol) of the nitro compound 2 was added to the solvent at 80 °C. The reaction was monitored by thin layer chromatography. After the reaction was completed, the cooled mixture was added to water and extracted with n-pentane. The organic phase was washed with a saturated sodium chloride solution, dried over sodium sulfate and evaporated. The residue was purified on silica gel.

Step 1.3

78 g (440 mmol) of N-bromosuccinimide (NBS) and 1 g of azobisisobutyronitrile were added to 25 g (176 mmol) of aromatic compound 3 dissolved in 250 ml of carbon tetrachloride. In the solution, carefully heat the mixture until the reaction begins. After the reaction was stopped, the reaction was boiled for 30 minutes. After cooling, the solid was separated and washed with carbon tetrachloride. The filtrate was evaporated and the residue was purified on silica gel.

Step 1.4

16.0 g (100 mmol) of diethyl malonate 5 and 30 g (100 mmol) of dibromide 4 were added to a suspension of 34.5 g (250 mmol) of potassium carbonate in 350 ml of ethyl methyl ketone. The mixture was boiled until the reaction was completely complete (monitored by thin layer chromatography). The solid was separated. The filtrate was evaporated and the residue was purified on silica gel.

Step 1.5

50 g (168 mmol) of malonic ester derivative 6 was added to a solution formed by dissolving 150 ml of ethanol and 50 ml of water in 22.4 g (400 mmol) of potassium hydroxide, and the mixture was heated under reflux until the ester was completely decomposed (thin layer chromatography layer). Analytical monitoring). The alcohol was then distilled off and the residue was acidified with semi-concentrated hydrochloric acid and extracted with methyl-t-butyl ether. The organic phase is evaporated. The residue was carefully heated to 150 °C. The reaction product was used in the next step without further purification.

Step 1.6

A solution of 60 ml (60 mmol) of 1 M borane-tetrahydrofuran complex in tetrahydrofuran was added to a solution of 10.3 g (52.0 mmol) of acid 7 in 60 ml of dichloromethane at 0 ° C under nitrogen. In the solution. At the time of addition, the temperature of the reaction solution was kept below 5 °C. The reaction was then heated to room temperature and. Then carefully add 130 ml of 1 N hydrochloric acid to the reaction vessel. The aqueous phase was extracted twice with DCM. The organic phase was dried and evaporated. The residue was purified on silica gel.

Step 1.7

9.6 g (44.4 mmol) of pyridinium chlorochromate was adsorbed under nitrogen to 60 g of strontium salt suspended in 50 ml of dichloromethane (Celite On top, a solution of 6.8 g (36.7 mmol) of alcohol 8 in 40 ml of DCM was added. When the reaction was complete, the solid was separated and washed with DCM. The eluate was washed with 1 N sodium hydroxide solution and 2 N hydrochloric acid and evaporated. The obtained residue was filtered through silica gel.

Step 1.8

25 g (137 mmol) of aldehyde 9 and 16.3 g (137 mmol) of 2-vinylpropanol 10 were dissolved in 140 ml of dichloromethane, and 31.4 g (69 mmol) of ruthenium (III) bromide was added. The reaction was allowed to go overnight at room temperature. The reaction was filtered through silica gel and then evaporated.

Step 1.9

40 g (111 mmol) of bromine compound 11 was dissolved in 165 ml of xylene under nitrogen atmosphere, and 38.5 ml of DBN was added. The mixture was boiled for 5 hours. Then 200 ml of water was added to the cooled reaction and acidified with dilute sulfuric acid. The organic phase was diluted with 300 ml of heptane, which was separated, washed with sodium bicarbonate and then evaporated. The residue obtained was filtered with tannin (toluene).

Step 1.10

20.0 g (71.9 mmol) of unsaturated piperane 12 was dissolved in 360 ml of methanol and 90 ml of toluene, hydrogenated over a (PPh ₃ ) ₃ RhCl catalyst at a pressure of 8 bar / temperature 80 ° C. The hydrogenation solution was evaporated and the residue of 13 was filtered with EtOAc (EtOAc/EtOAc).

98 ° C melting point.

△n 0.053△ε 13 γ1 68 mPa. s

A compound of the following formula was prepared in a manner similar to that of Example 1:

The following additional compounds were prepared according to the synthetic methods described:

Claims (9)

An indoline compound of the formula I, Wherein R ¹ represents H; an alkyl group having up to 15 carbon atoms which is unsubstituted, monosubstituted by CN or CF ₃ or at least monosubstituted by halogen, and one or more CHs of such alkyl groups ₂ groups can be independently independently -O-, -CH=CH-, -C≡C-, -S-, -CO-, -CO-O-, , -O-CO- or -O-CO-O- is displaced such that the oxygen atoms are not directly connected to each other; A ¹ and A ² are each independently, respectively representing (a) trans-1,4-cyclohexyl group In addition, one or more of the non-adjacent CH ₂ groups may be replaced by -O- and/or -S-, (b) a 1,4-phenylene group, and further, one or more of the CH groups The group may be substituted by N, (c) 1,4-cyclohexenyl, (d) selected from 1,4-bicyclo[2.2.2] octyl, piperidine-1,4-diyl, a group of cyclobutane-1,3-diyl, spiro[3.3]heptane-2,6-diyl, (e) a divalent group selected from the group consisting of Wherein Y, Y ¹ , Y ² and Y ³ are independent of each other, and may be H, F, Cl, CN, NCS, SF ₅ , OCF ₃ , OCHF ₂ , OCH ₂ F, OCH ₃ , CH ₃ , CH ₂ F, CHF ₂ or CF ₃ , one or more double bonds may be replaced by a single bond, and M, M ¹ or M ² may be -O-, -S-, -CH ₂ -, -CHF or -CF ₂ -, wherein the heteroatoms are mutually They are not directly bonded to each other, wherein the groups (a) to (d) may be substituted by one or more fluorine atoms, and if the group (e) is asymmetric, there may be two possible orientations; A divalent group of the formula: Z ¹ , Z ² or Z ³ are independent of each other and represent -CO-O-, -O-CO-, -CH ₂ O-, -OCH ₂ -, -CH ₂ CH ₂ -, -CH=CH-, -CH =CF-, -CF=CH-, -CF=CF-, -CHF-CHF-, -CH ₂ -CHF-, -CHF-CH ₂ -, -C≡C-, -(CH ₂ ) ₄ -, -CF ₂ O-, -OCF ₂ -, -C ₂ F ₄ -, -CH=CH-CH ₂ CH ₂ -, -CH ₂ CH ₂ OCF ₂ - or a single bond; X ¹ and X ² are independent of each other, Represents H, Cl, F, CN, NCS, SF ₅ or an alkyl group having up to 8 carbon atoms, in addition, one of the CH ₂ groups may be replaced by -O-, -CH=CH- or -C≡C- Wherein one or more hydrogen atoms may be replaced by F or Cl, and m, n are independent of each other, representing 0, 1 or 2, wherein m+n < 4. The compound of claim 1, which has the following formulas I1 to I13: Wherein R ¹ , X ¹ and X ² have the meanings as indicated in claim 1, and L ₁ and L ₂ represent H or F, respectively, independently of each other. The compound of claim 1 or 2, wherein X ¹ and X ² represent F. The compound of claim 1 or 2, wherein R ¹ represents an alkyl, alkoxy, alkenyl or alkenyloxy group having up to 7 carbon atoms. A process for the preparation of a compound of the formula I (wherein n represents 0) according to any one of claims 1 to 4, which comprises a dihydrofurfural of the formula V: (wherein X ¹ and X ² are as defined in claim 1) are reacted with but-3-en-1-ol as follows: Wherein R ¹ , A ¹ , Z ¹ and m are as defined in claim 1. A use of one or more compounds of the formula I according to any one of claims 1 to 4 as a component of a liquid-crystalline medium. A liquid crystal medium having at least two liquid crystal compositions characterized by containing at least one compound of formula I according to any one of claims 1 to 4. A liquid crystal display element characterized by containing the liquid crystal medium of claim 7. An electro-optical display element characterized by comprising a liquid crystal medium as in claim 7 as a dielectric.